WO2018030312A1 - PROCÉDÉ DE CROISSANCE DE CRISTAL (GaN) ET SUBSTRAT (GaN) EN PLAN (C) - Google Patents

PROCÉDÉ DE CROISSANCE DE CRISTAL (GaN) ET SUBSTRAT (GaN) EN PLAN (C) Download PDF

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WO2018030312A1
WO2018030312A1 PCT/JP2017/028483 JP2017028483W WO2018030312A1 WO 2018030312 A1 WO2018030312 A1 WO 2018030312A1 JP 2017028483 W JP2017028483 W JP 2017028483W WO 2018030312 A1 WO2018030312 A1 WO 2018030312A1
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Prior art keywords
gan
plane
gan substrate
pattern mask
crystal
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PCT/JP2017/028483
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English (en)
Japanese (ja)
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豊 三川
英夫 藤澤
多恵 望月
秀郎 浪田
紳一郎 川端
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三菱ケミカル株式会社
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Priority to JP2018533015A priority Critical patent/JP6981415B2/ja
Priority to CN201780048862.3A priority patent/CN109563641B/zh
Priority to CN202110907715.5A priority patent/CN113604885B/zh
Publication of WO2018030312A1 publication Critical patent/WO2018030312A1/fr
Priority to US16/270,454 priority patent/US10720326B2/en
Priority to US16/898,073 priority patent/US11404268B2/en

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    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02387—Group 13/15 materials
    • H01L21/02389—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/38—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • C30B29/406—Gallium nitride
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/06—Joining of crystals
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
    • C30B7/105—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes using ammonia as solvent, i.e. ammonothermal processes
    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/02433—Crystal orientation
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/0254—Nitrides
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02609—Crystal orientation
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02636—Selective deposition, e.g. simultaneous growth of mono- and non-monocrystalline semiconductor materials
    • H01L21/02639—Preparation of substrate for selective deposition
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02636—Selective deposition, e.g. simultaneous growth of mono- and non-monocrystalline semiconductor materials
    • H01L21/02639—Preparation of substrate for selective deposition
    • H01L21/02642—Mask materials other than SiO2 or SiN
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02636—Selective deposition, e.g. simultaneous growth of mono- and non-monocrystalline semiconductor materials
    • H01L21/02639—Preparation of substrate for selective deposition
    • H01L21/02645—Seed materials
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02636—Selective deposition, e.g. simultaneous growth of mono- and non-monocrystalline semiconductor materials
    • H01L21/02647—Lateral overgrowth
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
    • H01L21/2056—

Definitions

  • the present invention mainly relates to a GaN crystal growth method and a C-plane GaN substrate.
  • GaN gallium nitride
  • GaN single crystal substrates have attracted attention as semiconductor substrates for nitride semiconductor devices.
  • Nitride semiconductors are also called nitride-based III-V compound semiconductors, III-nitride compound semiconductors, GaN-based semiconductors, and the like, including GaN, and a part or all of GaN gallium in other periodic tables. Includes compounds substituted with Group 13 elements (B, Al, In, etc.).
  • the C-plane GaN substrate is a GaN single crystal substrate having a main surface parallel to the C-plane or slightly inclined from the C-plane.
  • the C-plane GaN substrate has a gallium polar surface that is the main surface on the [0001] side and a nitrogen polar surface that is the main surface on the [000-1] side. It is currently mainly gallium polar surfaces that are used to form nitride semiconductor devices. Examples of producing a C-plane GaN substrate from a GaN single crystal grown by an ammonothermal method have been reported (Non-patent Documents 1 and 2).
  • Patent Document 1 a GaN crystal is grown by an ammonothermal method on a C-plane GaN substrate provided with a stripe pattern mask.
  • NH 4 F ammonium fluoride
  • a GaN crystal film having a flat top surface and a thickness of 160 to 580 ⁇ m has grown through a pattern mask. It is not clear whether the pattern mask was formed on the gallium polar surface or the nitrogen polar surface.
  • Patent Document 2 a GaN single crystal is grown by an ammonothermal method on a C-plane GaN substrate provided with a stripe pattern mask on a nitrogen polar surface.
  • NH 4 F and NH 4 I are used in combination as mineralizers, and the GaN crystal does not coreless after passing through the pattern mask until the size in the c-axis direction is on the order of millimeters [ It has grown in the [000-1] direction.
  • Non-Patent Document 3 reports the growth rate of GaN crystals when various ammonium halide mineralizers are used in the ammonothermal method.
  • a main object of the present invention is to provide a novel method for growing a GaN crystal suitable as a material for a GaN substrate including a C-plane GaN substrate.
  • Another object of the present invention is to provide a novel C-plane GaN substrate that can be suitably used for the manufacture of nitride semiconductor devices and the like.
  • Embodiments of the present invention include the following.
  • the periodic opening pattern including the intersection is provided, and the longitudinal direction of at least a part of the linear opening is within ⁇ 3 ° from the direction of the line of intersection between the nitrogen polar surface and the M plane.
  • a GaN crystal growth method comprising: a third step in which a gap is formed.
  • the pattern mask includes the intersecting portion with a number density of 1 cm ⁇ 2 or more.
  • the pattern mask includes the intersecting portion with a number density of 20 cm ⁇ 2 or less.
  • the non-openings included in the unit pattern of the pattern mask are all square or hexagonal, and the pattern mask does not include a linear opening arranged at a pitch of less than 1 mm.
  • the pattern mask includes linear openings arranged at a pitch of 10 mm or less.
  • the pattern mask includes linear openings arranged at a pitch of 2 mm or less and linear openings arranged at a pitch of more than 2 mm, or linear openings arranged at a pitch of 3 mm or less; [11] including linear openings arranged at a pitch exceeding 3 mm, or linear openings arranged at a pitch of 4 mm or less, and linear openings arranged at a pitch exceeding 4 mm.
  • the growth method as described in. [14] The growth method according to [13], wherein the pattern mask includes linear openings arranged at a pitch exceeding 4 mm.
  • the periodic opening pattern is a square lattice pattern, and in the second step, a first linear opening and a second linear opening having different longitudinal directions are provided in the pattern mask.
  • [14] The growth method according to any one of [14].
  • [16] The growth method according to [15], wherein one of the pitch between the first linear openings and the pitch between the second linear openings is 1.5 times or more of the other.
  • [17] The growth method according to any one of [1] to [16], wherein in the third step, a void is formed between the GaN crystal and the pattern mask.
  • [18] The growth method according to [17], wherein in the third step, the GaN crystal is grown so that no through hole remains above the non-opening portion of the pattern mask.
  • a method for producing a C-plane GaN substrate comprising the steps of growing a GaN crystal using the growth method according to any one of [1] to [21] and processing the grown GaN crystal. .
  • At least one main surface has a plurality of dislocation arrays periodically arranged, and excluding the plurality of dislocation arrays, has a dislocation group that periodically exists on the one main surface.
  • a C-plane GaN substrate characterized in that the substrate is a non-existent substrate, and each of the plurality of dislocation arrays is derived from coalescence generated during growth of a GaN crystal constituting the substrate.
  • the C-plane GaN substrate according to [24] wherein the dislocation arrays are two-dimensionally arranged on the main surface.
  • At least one main surface has a plurality of dislocation arrays periodically and two-dimensionally arranged, and excluding the plurality of dislocation arrays, a dislocation group periodically present on the one main surface is C-plane GaN substrate that does not have.
  • the C-plane GaN substrate according to [27] wherein the dislocation arrays on the main surface have periodicity in two or more directions.
  • the C-plane GaN substrate according to [31] containing F and I.
  • [42] including a step of preparing the C-plane GaN substrate according to any one of [24] to [41] and a step of epitaxially growing one or more types of nitride semiconductors on the prepared C-plane GaN substrate.
  • a method for manufacturing a nitride semiconductor device. [43] including a step of preparing the C-plane GaN substrate according to any one of [24] to [41] and a step of epitaxially growing one or more nitride semiconductors on the prepared C-plane GaN substrate. Epitaxial substrate manufacturing method.
  • a GaN layer bonded substrate comprising: preparing the C-plane GaN substrate according to any one of [24] to [41]; and bonding the prepared C-plane GaN substrate to a different composition substrate. Manufacturing method.
  • a novel method is provided for growing GaN crystals suitable as materials for GaN substrates including C-plane GaN substrates.
  • a novel C-plane GaN substrate that can be suitably used for manufacturing a nitride semiconductor device or the like is provided.
  • FIG. 1 is a flowchart of a GaN crystal growth method according to an embodiment.
  • FIG. 2A is a perspective view showing a GaN seed
  • FIG. 2B is a perspective view showing the GaN seed after a pattern mask is arranged on a nitrogen polar surface.
  • FIG. 3 is a plan view showing a part of the GaN seed on the nitrogen polar surface side after the pattern mask is arranged.
  • 4 (a) to 4 (d) are plan views showing GaN seeds in which a pattern mask is arranged on a nitrogen polar surface, respectively.
  • FIGS. 5E to 5H are plan views each showing a GaN seed in which a pattern mask is arranged on a nitrogen polar surface.
  • FIGS. 5E to 5H are plan views each showing a GaN seed in which a pattern mask is arranged on a nitrogen polar surface.
  • FIGS. 6 (i) to 6 (l) are plan views each showing a GaN seed in which a pattern mask is arranged on a nitrogen polar surface.
  • FIGS. 7A to 7F are plan views each showing a part of a pattern mask formed on the nitrogen polar surface of the GaN seed.
  • FIGS. 8A to 8F are plan views each showing a part of a pattern mask formed on the nitrogen polar surface of the GaN seed.
  • FIGS. 9A to 9E are cross-sectional views showing a process of growing a GaN crystal.
  • FIG. 10A is a plan view showing a part of the GaN seed on the nitrogen polar surface side after the pattern mask in which the linear openings form continuous intersections is arranged, and FIG. FIG.
  • FIG. 11 is a plan view showing a GaN crystal in an initial growth stage grown through the pattern mask shown in FIG.
  • FIG. 11A is a plan view showing a part of the nitrogen polar surface side of the GaN seed after the pattern mask in which the linear openings form discontinuous intersections is arranged
  • FIG. 12 is a cross-sectional fluorescence microscope image (drawing substitute photograph) of a GaN crystal grown in an ammonothermal manner through a pattern mask on the nitrogen polar surface of the GaN seed.
  • FIG. 13 is a cross-sectional fluorescence microscope image (drawing substitute photograph) of a GaN crystal grown in an ammonothermal manner through a pattern mask on the nitrogen polar surface of the GaN seed.
  • FIG. 14 is a cross-sectional fluorescence microscope image (drawing substitute photograph) of a GaN crystal grown in an ammonothermal manner through a pattern mask on the nitrogen polar surface of the GaN seed.
  • FIG. 15 shows a crystal growth apparatus that can be used for the growth of GaN crystals by the ammonothermal method.
  • FIGS. 16A and 16B are cross-sectional views each showing a position where the GaN crystal is sliced.
  • FIG. 17 shows a shape example of the C-plane GaN substrate according to the embodiment, FIG. 17A is a perspective view, and FIG. 17B is a side view.
  • the crystal axis parallel to [0001] and [000-1] is the c axis
  • the crystal axis parallel to ⁇ 10-10> is the m axis
  • the crystal axis parallel to ⁇ 11-20> is the a axis.
  • the crystal plane orthogonal to the c-axis is referred to as C-plane (C-plane)
  • the crystal plane orthogonal to the m-axis is referred to as M-plane (M-plane)
  • the crystal plane orthogonal to the a-axis is referred to as A-plane.
  • GaN Crystal Growth Method A flowchart of a GaN crystal growth method according to an embodiment is shown in FIG.
  • This GaN crystal growth method includes the following steps S1 to S3 which are sequentially executed.
  • S1 preparing a GaN seed having a nitrogen polar surface.
  • S2 A step of arranging a pattern mask on the nitrogen polar surface of the GaN seed prepared in step S1.
  • S3 Amorphous growth of GaN crystals on the nitrogen polar surface of the GaN seed prepared in step S1 through the pattern mask arranged in step S2. Details of steps S1 to S3 will be described below.
  • Step S1 is a step of preparing a GaN seed having a nitrogen polar surface.
  • a typical example of a GaN seed is a C-plane GaN substrate.
  • the main surface on the [0001] side is a gallium polar surface
  • the main surface on the [000-1] side is a nitrogen polar surface.
  • a preferable GaN seed is a C-plane GaN substrate obtained by processing a bulk GaN crystal grown by an HVPE method or an acidic ammonothermal method. It may be made from a bulk GaN crystal grown by the method described in the section.
  • a dot core (dot-like domain with reversed polarity) is formed in the GaN crystal to be grown, and the arrangement of the dot core is changed in the subsequent step S2. It sets so that it may not overlap with the opening pattern provided in the pattern mask.
  • the orientation of the nitrogen polar surface of the GaN seed is preferably within 2 ° from [000-1] when expressed in the direction of the normal vector. This means that the angle between the normal vector of the nitrogen polar surface and [000-1] is within 2 °.
  • the orientation of the nitrogen polar surface of the GaN seed is more preferably within 1 ° from [000-1]. Area of the N-polar surface of the GaN seed, 15cm 2 50cm or more than 2, 50cm 2 or more 100cm less than 2, 100cm 2 or more 200cm less than 2, 200cm 2 or more 350cm less than 2, 350cm 2 or more 500cm less than 2, 500cm 2 or more 750 cm 2 Or less.
  • the nitrogen polar surface of the GaN seed When the nitrogen polar surface of the GaN seed is circular, its diameter is usually 45 mm or more and 305 mm or less. The diameter is typically 45-55 mm (about 2 inches), 95-105 mm (about 4 inches), 145-155 mm (about 6 inches), 195-205 mm (about 8 inches), 295-305 mm (about 12 inches).
  • the thickness when the GaN seed is a C-plane GaN substrate having a diameter of 50 mm, the thickness is preferably 300 ⁇ m or more. If the diameter is larger than this, the preferable lower limit value of the thickness is also increased. There is no particular upper limit to the thickness of the GaN seed, but it is usually 20 mm or less.
  • the size of the GaN seed is determined in consideration of the size of the GaN crystal to be grown in the subsequent step S3. For example, when a C-plane GaN substrate having a size of 45 mm in all of the [1-100] direction, [10-10] direction, and [01-10] direction is to be cut out from a GaN crystal to be grown, Must be grown so that the sizes in the [1-100] direction, [10-10] direction, and [01-10] direction are all 45 mm or more.
  • the [1-100] direction, [10 ⁇ 10] direction and [01-10] direction are preferably 45 mm or more in size.
  • the nitrogen polar surface of the GaN seed is usually planarized by polishing or grinding.
  • the damaged layer introduced by the planarization process is removed from the nitrogen polar surface by CMP (Chemical Mechanical Polishing) and / or etching.
  • a pattern mask is placed on the nitrogen polar surface of the GaN seed prepared in step S1.
  • the material forming the surface of the pattern mask is preferably a platinum group metal, that is, a metal selected from Ru (ruthenium), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and Pt (platinum). And particularly preferably Pt.
  • the pattern mask may be a single layer film made of a platinum group metal or an alloy thereof, but is preferably a platinum group as a surface layer on an underlayer made of a metal having better adhesion to a GaN crystal than the platinum group metal. It is a multilayer film formed by laminating metal layers. Examples of the material for the underlayer include, but are not limited to, W (tungsten), Mo (molybdenum), Ti (titanium), and alloys containing one or more selected from these.
  • the pattern mask is provided with a periodic opening pattern composed of linear openings, particularly a periodic opening pattern including an intersection.
  • FIG. 2A is a perspective view showing an example of a GaN seed.
  • the GaN seed 10 is a disc-shaped C-plane GaN substrate, and has a nitrogen polar surface 11, a gallium polar surface 12, and side surfaces 13.
  • FIG. 2B is a perspective view showing the GaN seed 10 after the pattern mask 20 is arranged on the nitrogen polar surface 11.
  • the pattern mask 20 is provided with a square lattice pattern composed of linear openings 21.
  • FIG. 3 is a plan view showing a part of the GaN seed 10 on the nitrogen polar surface 11 side after the pattern mask 20 is arranged.
  • the pattern mask 20 is provided with a linear opening 21, and the nitrogen polar surface 11 of the GaN seed is exposed inside the linear opening 21.
  • the plurality of first linear openings 211 and the plurality of second linear openings 212 form a square lattice pattern.
  • the pitch P 1 between the first linear openings 211 and the pitch P 2 between the second linear openings 212 are constant.
  • the pitch means the distance between the center lines between the linear openings adjacent to each other across the non-opening portion of the pattern mask.
  • the pitch P 1 and the pitch P 2 may be the same or different. The inventors have found empirically that when the pitch P 1 and the pitch P 2 are different from each other on the non-opening portion of the pattern mask when the GaN crystal is grown in the subsequent step S3. The resulting through hole tends to be easily blocked. Therefore, one of the pitches P 1 and P 2 is preferably 1.5 times or more of the other and more preferably 2 times or more.
  • the orientation of the first linear opening 211 and the second linear opening 212 is such that one of the directions of the intersection of the nitrogen polar surface 11 of the GaN seed and the M plane is the first reference direction, and the other is the second reference direction. It is convenient to express.
  • the first reference direction is the direction of the line of intersection between the nitrogen polar surface 11 and the (1-100) plane
  • the second reference direction is the nitrogen polar surface 11 and the (10-10) plane or (01- 10) The direction of the line of intersection with the surface.
  • the angle theta 1 is within ⁇ 3 °.
  • the longitudinal direction in the portion of 50% or more of the total extension of the linear opening 21 is preferably within ⁇ 3 ° from the direction of the line of intersection between the nitrogen polar surface of the GaN seed and the M plane.
  • both the angle ⁇ 1 and the angle ⁇ 2 are within ⁇ 3 °, that is, the longitudinal direction in all portions of the linear opening 21 is the direction of the intersection line between the nitrogen polar surface of the GaN seed and the M plane.
  • the angles ⁇ 1 and ⁇ 2 are more preferably within ⁇ 2 °, and still more preferably within ⁇ 1 °.
  • the square lattice pattern provided in the pattern mask 20 includes an intersection K formed between the first linear opening 211 and the second linear opening 212.
  • the number density of the intersections included in the pattern mask is preferably 1 cm ⁇ 2 or more.
  • the GaN crystal grown in the subsequent step S3 becomes a GaN seed.
  • the number density is preferably 20 cm ⁇ 2 or less, more preferably 15 cm ⁇ 2 or less, and more preferably 10 cm ⁇ 2 or less in consideration of an increase in dislocation defects inherited from.
  • the line widths W 1 and W 2 are each preferably 0.5 mm or less, more preferably 0.2 mm or less, and even more preferably 0.1 mm or less.
  • the line width W 2 of the line width W 1 and the second linear opening 212 of the first linear opening 211 preferably has reasonably wide. This is because the growth rate in the initial stage is higher when the GaN crystal is grown in the subsequent step S3. Accordingly, the line widths W 1 and W 2 are each preferably 5 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 40 ⁇ m or more.
  • the pitch P 1 between the first linear openings 211 and the pitch P 2 between the second linear openings 212 are larger. It is advantageous. Accordingly, the pitches P 1 and P 2 are preferably 1 mm or more, more preferably 2 mm or more, more preferably 3 mm or more, and more preferably 4 mm or more.
  • one or both of pitches P 1 and P 2 can be 4 mm or less, further 3 mm or less, and further 2 mm or less. In a preferred example, only one of the pitches P 1 and P 2 can be set to 4 mm or less, 3 mm or less, or 2 mm or less in consideration of both reduction of dislocation defects to be inherited and improvement of manufacturing efficiency.
  • the periodic opening pattern that can be provided in the pattern mask arranged on the GaN seed in step S2 is not limited to the square lattice pattern.
  • Each of the drawings included in FIGS. 4 to 6 is a plan view showing the GaN seed after the pattern mask is disposed on the nitrogen polar surface, and illustrates various periodic opening patterns that can be provided in the pattern mask.
  • the opening pattern that can be employed is not limited to these.
  • the linear openings 21 form a zigzag stripe pattern.
  • FIG. 4B the linear openings 21 form a kind of lattice pattern.
  • the linear opening 21 forms the inclined brick lattice pattern.
  • FIG. 4D the linear openings 21 form an inclined square lattice pattern.
  • FIG. 5 (e) the linear openings 21 form a herringbone lattice pattern.
  • the linear opening 21 forms the lattice pattern which compromised the inclined brick lattice and the inclined square lattice.
  • the linear openings 21 form a triangular lattice pattern.
  • the linear openings 21 form a flat honeycomb lattice pattern.
  • the linear openings 21 form a Bishamon turtle shell lattice pattern.
  • the linear openings 21 form a cubic pattern.
  • the linear openings 21 form a Y-shaped pattern.
  • the periodic opening pattern provided in the pattern mask 20 includes an intersection.
  • a crossing portion in which two or more linear openings having different longitudinal directions are connected is referred to as a continuous crossing portion, including those shown in FIGS. 7 (a) to (f).
  • the intersections referred to in this specification include not only continuous intersections but also discontinuous intersections exemplified in FIGS. 8A to 8F.
  • a discontinuous intersection can be regarded as an intersection formed by adding a change that disconnects the connection between the linear openings to the continuous intersection.
  • the distance between two linear openings separated by a non-opening at a discontinuous intersection is 300 ⁇ m or less, preferably 200 ⁇ m or less.
  • the arrangement of the intersections in the periodic opening pattern is two-dimensional. If the periodic opening pattern includes an intersection, the through-hole generated above the non-opening of the pattern mask is likely to be blocked when the GaN crystal is grown in the subsequent step S3. This effect is remarkable when the arrangement of the intersections in the periodic opening pattern is two-dimensional, and becomes more remarkable by increasing the number density of the intersections. Therefore, the arrangement of the intersections in the periodic aperture pattern is preferably two-dimensional, and the number density of the intersections included in the pattern mask at that time is preferably 1 cm ⁇ 2 or more.
  • the number density at the intersection is preferably 20 cm ⁇ 2 or less, more preferably 15 cm ⁇ 2 or less, and more preferably 10 cm ⁇ 2 or less.
  • a preferred design regarding the orientation, line width, and pitch of the linear openings when the various periodic opening patterns shown in FIGS. 4 to 6 are provided in the pattern mask is as follows. At least a part of the linear opening has a longitudinal direction within ⁇ 3 ° from the direction of the line of intersection between the nitrogen polar surface of the GaN seed and the M plane. More preferably, in the portion that occupies 50% or more of the total extension of the linear opening, and in all the portions of the linear opening, the longitudinal direction intersects the nitrogen polar surface of the GaN seed and the M plane. It is within ⁇ 3 ° from the direction of the line.
  • the line width of the linear opening is preferably 0.5 mm or less, more preferably 0.2 mm or less, more preferably 0.1 mm or less, and preferably 5 ⁇ m or more, More preferably, it is 20 ⁇ m or more, and more preferably 40 ⁇ m or more.
  • the line width need not be the same in all portions of the linear opening.
  • the pattern mask preferably does not include a linear opening arranged at a pitch of less than 1 mm, and arranged at a pitch of less than 2 mm. More preferably, it does not include the linear openings arranged at a pitch of less than 3 mm, more preferably does not include the linear openings arranged at a pitch of less than 4 mm, and more preferably does not include the linear openings arranged at a pitch of less than 4 mm. .
  • the pattern mask includes linear openings arranged at a pitch of 10 mm or less, and further, linear patterns arranged at a pitch of 4 mm or less, 3 mm or less, or 2 mm or less.
  • An opening may be included.
  • the pattern mask is provided with linear openings arranged with a pitch of 1 mm or more and 4 mm or less and linear openings arranged with a pitch of over 4 mm, or with a pitch of 1 mm or more and 3 mm or less.
  • a linear opening may be provided.
  • the pattern mask may be provided with linear openings arranged at a pitch exceeding 4 mm.
  • the non-openings included in the unit pattern of the pattern mask are all quadrangular because of FIGS. 4 (c) and (d), FIGS. 5 (e) and (f), FIG. 6 (j) and (k).
  • all the non-openings included in the unit pattern of the pattern mask are hexagonal.
  • Step S3 In Step S3, a GaN crystal is grown ammonothermally through the pattern mask arranged in Step S2 on the nitrogen polar surface on the GaN seed prepared in Step S1.
  • the GaN crystal growth process in step S3 will be described with reference to FIG.
  • FIG. 9A is a cross-sectional view showing a state before crystal growth starts.
  • a pattern mask 20 having a linear opening 21 is provided on the nitrogen polar surface 11 of the GaN seed 10.
  • FIG. 9B shows that the GaN crystal 30 has started to grow on the nitrogen polar surface 11 exposed inside the linear opening 21 provided in the pattern mask 20.
  • the GaN crystal 30 After passing through the pattern mask 20, the GaN crystal 30 grows not only in the [000-1] direction but also in the lateral direction (direction parallel to the nitrogen polar surface 11) as shown in FIG. A gap G is formed between the crystal 30 and the pattern mask 20. As a result, disorder of orientation of the GaN crystal 30 that may occur due to contact with the pattern mask 20 is reduced.
  • the GaN crystal 30 has a through hole T above the non-opening portion of the pattern mask 20.
  • the gap G is gradually filled, but is not completely filled, and the through hole T is closed with the void V remaining as shown in FIG.
  • the GaN crystal 30 is further grown in the [000-1] direction as shown in FIG. It is considered that the stress generated between the GaN seed 10 and the GaN crystal 30 is relaxed by the void V, and consequently, the strain of the GaN crystal 30 is reduced.
  • the growth amount in the [000-1] direction of the GaN crystal 30 after the through hole T is closed is preferably 1 mm or more, more preferably 2 mm or more, more preferably 3 mm or more, and there is no particular upper limit. Note that in step S3, the GaN crystal grows also on the gallium polar surface 12 of the GaN seed 10, but is not shown in FIG.
  • dislocation array appears on the main surface of the C-plane GaN substrate cut out from the GaN crystal formed in the stage of FIG.
  • the shape of the dislocation array is roughly the shape of an intersection formed by an extended surface obtained by extending the coreless surface in the [000-1] direction and the main surface of the C-plane GaN substrate.
  • the line of intersection may include straight portions, curved portions, bends and branches.
  • the dislocation array can be said to be a trace showing where coalescence has occurred during the growth process of the GaN crystal constituting the C-plane substrate.
  • a closed non-opening is a non-opening that is surrounded by a linear opening.
  • the pattern mask has a closed non-opening portion as shown in FIGS. 4 (c) and (d), FIGS. 5 (e) to (h), and FIGS. (K).
  • the arrangement of closed non-openings in the pattern mask is periodic and two-dimensional.
  • FIG. 10A is a plan view showing a part of the GaN seed on the nitrogen polar surface side where a pattern mask in which linear openings form intersections is arranged.
  • the pattern mask 20 is provided with a first linear opening 211 and a second linear opening 212 having different longitudinal directions, and a continuous intersection is formed between the two types of linear openings.
  • FIG. 10B shows a state in which the GaN crystal 30 in the growth stage of FIG. 9C is formed on the GaN seed shown in FIG. The GaN crystal 30 grows along the linear opening 21. What is indicated by a broken line is the outline of the opening 21 hidden under the GaN crystal 30.
  • Each of the four arrows in FIG. 10B indicates a recessed portion formed on a side portion of the GaN crystal 30 that grows on the intersection formed by the linear openings 211 and 212. The direction of the arrow represents the recessed direction of the recessed portion.
  • the formation of the recessed portion causes a re-entrant angle effect, and the GaN crystal 30 is prompted to grow in the direction opposite to the arrow. That is, the driving force for growing the GaN crystal so as to close the through hole formed above the non-opening portion of the pattern mask is generated by the concave angle effect.
  • FIG. 11A is a plan view showing a part of the GaN seed on the nitrogen polar surface side where a pattern mask in which the linear openings form discontinuous intersections is arranged.
  • a discontinuous intersection is formed by the first linear opening 211 and the second linear opening 212 divided into two.
  • a recessed portion indicated by an arrow is formed on the side portion of the GaN crystal 30 growing on the discontinuous intersection.
  • the resulting dip angle effect encourages the GaN crystal 30 to grow in the direction opposite the arrow.
  • FIGS. 12 to 14 are cross-sectional fluorescence microscopic images of GaN crystals grown ammonothermally through a pattern mask on the nitrogen polar surface of the GaN seed, respectively.
  • the longitudinal direction of the linear opening was inclined by about 12 ° from the direction of the intersection of the nitrogen polar surface of the GaN seed and the M plane.
  • the longitudinal direction of the linear opening was inclined by 6 ° from the direction of the intersecting line.
  • the longitudinal direction of the linear opening was parallel to the intersecting line.
  • the darkest part is the cross section of the GaN seed. Since this GaN seed is made of a GaN crystal having a low point defect density grown by the HVPE method, it looks dark in a fluorescence microscope image. The inverted trapezoidal depressions seen on the surface of the GaN seed are thought to have been formed by partially etching back the GaN seed at the opening of the pattern mask before the monothermal growth of the GaN crystal began. It is done. The width of the recess is wider than the line width of the linear opening provided in the pattern mask, and it can be seen that the etching progressed in the lateral direction below the pattern mask.
  • a GaN crystal grown monomonothermally on a GaN seed appears brighter than a GaN seed because of its relatively high point defect density.
  • the inside of the above-mentioned inverted trapezoidal depression formed on the GaN seed surface is buried with a growth crystal.
  • the N-plane growth region R1 is a region made of a GaN crystal grown using the N-plane, that is, the (000-1) surface as the growth surface, and the propagation direction of threading dislocations in the inside is the [000-1] direction.
  • the lateral growth region R2 is a region made of a GaN crystal grown with the crystal surface inclined with respect to the (000-1) surface as the growth surface, and the propagation direction of threading dislocations in the inside is in the [000-1] direction. Inclined.
  • the difference in contrast between the N-plane growth region R1 and the lateral growth region R2 is caused by the difference in growth surface, that is, impurities and / or defects caused by the difference in the crystal surface exposed when each region is formed. Reflects the difference in concentration.
  • the formation of the N-plane growth region R1 starts immediately after the inside of the inverted trapezoidal depression in the GaN seed surface is buried, and the N-plane growth region R1 is in the [000-1] direction. It continues without interruption. Therefore, it is considered that the threading dislocation inherited from the GaN seed to the growth crystal reaches the upper part of the growth crystal without changing the propagation direction.
  • the N-plane growth region R1 and the lateral growth region R2 are observed in the grown crystal, as in FIG.
  • the N-plane growth region R1 starting from the vicinity of the opening of the pattern mask is constricted. For this reason, a part of threading dislocations inherited from the GaN seed to the grown crystal may be bent at the constricted portion of the N-plane growth region R1 to change the propagation direction. However, it is estimated that the number is not large.
  • a crystal growth apparatus 100 includes an autoclave 101 and a Pt capsule 102 installed therein.
  • the capsule 102 has a raw material dissolution zone 102a and a crystal growth zone 102b that are partitioned by a baffle 103 made of Pt.
  • a feedstock FS is placed in the raw material melting zone 102a.
  • a seed S suspended by a Pt wire 104 is installed in the crystal growth zone 102b.
  • a gas line to which the vacuum pump 105, the ammonia cylinder 106 and the nitrogen cylinder 107 are connected is connected to the autoclave 101 and the capsule 102 via the valve 108.
  • NH 3 ammonia
  • the amount of NH 3 supplied from the ammonia cylinder 106 can be confirmed with the mass flow meter 109.
  • polycrystalline GaN produced by a method of reacting gaseous GaCl obtained by bringing HCl (hydrogen chloride) gas into contact with simple substance Ga (metal gallium) under heating and NH 3 gas is preferably used.
  • Mineralizers for promoting the dissolution of the feedstock include one or more ammonium halides selected from NH 4 Cl (ammonium chloride), NH 4 Br (ammonium bromide) and NH 4 I (ammonium iodide).
  • NH 4 F is preferably used in combination. Particularly preferably, NH 4 F and NH 4 I are used in combination. When using a growth temperature of 650 ° C.
  • NH 3 is also introduced into the space between the autoclave 101 and the capsule 102 and then heated by a heater (not shown) from the outside of the autoclave 101, The inside is set to a supercritical state or a subcritical state. Etching also occurs on the surface of the seed S until the feedstock FS is sufficiently dissolved and the solvent reaches saturation. If necessary, for the purpose of promoting the etch back of the seed S, an inversion period in which the temperature gradient between the raw material melting zone 102a and the crystal growth zone 102b is reversed from that at the time of crystal growth is set before the start of growth. It can also be provided.
  • the growth temperature is preferably 550 ° C. or higher.
  • the growth pressure can be set, for example, within a range of 100 to 250 MPa, but is not limited thereto.
  • NH 4 F and NH 4 I are used as mineralizers so that the molar ratios to NH 3 are 0.5% and 4.0%, respectively, the pressure is about 220 MPa, and the temperature Ts of the raw material dissolution zone GaN can be grown under the condition that the average value of the temperature Tg of the crystal growth zone is about 600 ° C. and the temperature difference Ts ⁇ Tg between these two zones is about 5 ° C. (Ts> Tg).
  • NH 4 F and NH 4 I are used as mineralizers so that the molar ratio to NH 3 is 1.0%, the pressure is about 220 MPa, the temperature Ts of the raw material dissolution zone and the crystal growth GaN can be grown under the condition that the average temperature Tg of the zones is about 605 to 610 ° C. and the temperature difference Ts ⁇ Tg between these two zones is about 5 to 10 ° C. (Ts> Tg). It is possible to increase the growth rate of the GaN crystal by increasing the temperature difference between the raw material dissolution zone and the crystal growth zone. However, if the growth rate is too high, the growth of the GaN crystal is shown in FIG. There is a problem that it is difficult to proceed from the stage of FIG. 9D to the stage of FIG. 9D, that is, it is difficult to close the through hole of the GaN crystal. In step S3, every time the feedstock is used up, the capsule can be replaced and the GaN crystal regrowth can be repeated.
  • the GaN crystal to be grown it may be doped with O (oxygen), Si (silicon), Ge (germanium), S (sulfur) or the like.
  • O oxygen
  • Si silicon
  • Ge germanium
  • S sulfur
  • the n-type carrier concentration of the GaN crystal is 20 to 70% of the O concentration, which is lower than 30%. Also often. Therefore, in order to obtain a GaN crystal having an n-type carrier concentration of, for example, 1 ⁇ 10 18 cm ⁇ 3 or more, O is added at a concentration of at least 2 ⁇ 10 18 atoms / cm 3 , preferably 4 ⁇ 10 18 atoms / cm 3 or more. Added.
  • O is introduced in the form of moisture in a growth vessel (capsule 102 in the example of FIG. 15) or polycrystalline GaN used for feedstock.
  • the GaN crystal to be grown semi-insulating it may be doped with iron (Fe), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), magnesium (Mg) or the like.
  • GaN substrates having various plane orientations can be manufactured.
  • the processing may include slicing the GaN crystal using a slicer such as a single wire saw or a multi-wire saw.
  • the slice thickness can be appropriately determined according to the purpose, but is usually 100 ⁇ m or more and 20 mm or less.
  • the planarization of the cut surface of the GaN crystal can be performed by either or both of grinding and lapping. Removal of the damaged layer from the cut surface can be performed by one or both of CMP and etching.
  • a planar GaN substrate is obtained.
  • Such a substrate can be suitably used as a substrate for a semiconductor device, can be used for manufacturing a GaN layer bonded substrate, and can be used as a seed for growing a bulk GaN crystal by various crystal growth techniques.
  • the C-plane GaN substrate obtained by slicing the GaN crystal 30 at the position indicated by the broken line in FIG. 16B has a through hole in the main surface, and thus is not suitable for use as a substrate for a semiconductor device.
  • F can be used as a seed when growing a bulk GaN crystal in an ammonothermal manner using an acidic mineralizer containing F. This is because if the acidic mineralizer contains F, a GaN crystal grows so as to block even if there is a through hole in the seed.
  • step S3 the growth of the GaN crystal 30 does not completely proceed to the stage of FIG. 9D, that is, in a state where all or part of the through hole T remains unclosed.
  • the growth of can also be terminated.
  • This C-plane GaN substrate is obtained by using an acidic mineralizer containing F. It can be used as a seed when growing bulk GaN crystals in an ammonothermal manner.
  • the C-plane GaN substrate according to the embodiment includes the above-described 1. It can be produced by processing a GaN crystal grown using the GaN crystal growth method described in the section. 2.1. Shape and Size
  • the C-plane GaN substrate of the embodiment includes a main surface on one side and a main surface on the opposite side, and the thickness direction is parallel or substantially parallel to the c-axis.
  • One of the two main surfaces is a nitrogen polar surface and the other is a gallium polar surface.
  • FIG. 17 illustrates the shape of the C-plane GaN substrate of the embodiment, where FIG.
  • the C-plane GaN substrate 40 has a disk shape, and includes a nitrogen polar surface 41 which is a main surface on the [000-1] side and a gallium polar surface 42 which is a main surface on the [0001] side.
  • the shape is circular.
  • the nitrogen polar surface 41 and the gallium polar surface 42 are connected via a side surface 43.
  • the area of the main surface of the C-plane GaN substrate according to the embodiment is 15 cm 2 or more and less than 50 cm 2 , 50 cm 2 or more and less than 100 cm 2 , 100 cm 2 or more and less than 200 cm 2 , 200 cm 2 or more and less than 350 cm 2 , 350 cm 2 or more and less than 500 cm 2. , and the like 500 cm 2 or more 750cm less than 2.
  • the orientation of the gallium polar surface is within 10 ° from [0001].
  • the orientation of the gallium polar surface is preferably within 5 °, more preferably within 2 °, more preferably within 1 ° from [0001].
  • the orientation of the nitrogen polar surface is within 10 ° from [000-1], preferably within 5 °, more preferably within 2 °, more preferably within 1 °.
  • the gallium polar surface and the nitrogen polar surface are preferably parallel to each other.
  • the diameter is usually 45 mm or more and 305 mm or less.
  • the diameter is typically 45-55 mm (about 2 inches), 95-105 mm (about 4 inches), 145-155 mm (about 6 inches), 195-205 mm (about 8 inches), 295-305 mm (about 12 inches).
  • the thickness of the C-plane GaN substrate according to the embodiment is usually 100 ⁇ m or more, 150 ⁇ m or more and less than 250 ⁇ m, 250 ⁇ m or more and less than 300 ⁇ m, 300 ⁇ m or more and less than 400 ⁇ m, 400 ⁇ m or more and less than 500 ⁇ m, 500 ⁇ m or more and less than 750 ⁇ m, 750 ⁇ m or more and less than 1 mm, 1 mm For example, it may be less than 2 mm, 2 mm or more and less than 5 mm. Although there is no upper limit in particular in this thickness, it is usually 20 mm or less.
  • the boundary between the gallium polar surface and the side surface may be chamfered.
  • the C-plane GaN substrate according to the embodiment has various markings as required, such as an orientation flat or notch for displaying the crystal orientation, and an index flat for facilitating discrimination between the gallium polar surface and the nitrogen polar surface. Can be provided.
  • the C-plane GaN substrate of the embodiment may have a group of linearly arranged dislocations, that is, a dislocation array on the main surface.
  • the dislocation here is an end point of threading dislocation (edge dislocation, spiral dislocation, and mixed dislocation).
  • a plurality of dislocation arrays may be periodically arranged on the main surface of the C-plane GaN substrate of the embodiment.
  • the arrangement of the plurality of dislocation arrays may be two-dimensional, and may have periodicity in two or more directions.
  • dislocation arrays on the main surface of the C-plane GaN substrate should be confirmed with an optical microscope by etching the main surface under appropriate conditions and forming etch pits at the end points of threading dislocations. Is possible.
  • the confirmation may be performed on at least one of a gallium polar surface and a nitrogen polar surface. In the case of a gallium polar surface, etching for 1 hour or longer using 89% sulfuric acid heated to 270 ° C. as an etchant can form etch pits corresponding to all kinds of threading dislocations existing on the surface. it can.
  • the above 1.
  • the pattern mask is not opened on the main surface of the C-plane GaN substrate in step S3.
  • dislocation arrays derived from the coalescence occurring above.
  • a pattern mask having a closed non-opening is formed on the GaN seed in step S2
  • a dislocation array corresponding to the non-opening appears on the main surface of the obtained C-plane GaN substrate.
  • the C-plane substrate manufactured from the GaN crystal grown using the GaN crystal growth method described in the above section may have a plurality of dislocation arrays periodically arranged on the main surface.
  • the arrangement of the plurality of dislocation arrays may be two-dimensional, and may have periodicity in two or more directions.
  • step S2 only a linear opening parallel to the intersection line between the nitrogen polar surface of the GaN seed and the M plane can be provided in the pattern mask.
  • the dislocation array that the C-plane GaN substrate obtained from the GaN crystal grown in step S3 has on the main surface can be only a dislocation array derived from coalescence occurring above the non-opening portion of the pattern mask in step S3.
  • the above 1.
  • the periodic pattern mask provided on the GaN seed in step S2
  • the opening pattern is composed of only linear openings parallel to the intersection of the nitrogen polar surface of the GaN seed and the M plane
  • the surface of the C-plane GaN substrate manufactured from the GaN crystal grown in step S3 In addition, a periodic pattern composed of dislocations inherited from the GaN seed is not observed.
  • a periodic opening pattern of a pattern mask provided on the same GaN seed is not formed as in the embodiment of the present invention, and a linear opening inclined by about 12 ° from the intersection line between the nitrogen polar surface of the GaN seed and the M plane.
  • a periodic pattern composed of dislocations inherited from the GaN seed is observed on the surface of the resulting C-plane GaN substrate. This periodic pattern is substantially the same pattern as the periodic opening pattern of the pattern mask.
  • the C-plane GaN substrate of the embodiment can be any of n-type conductivity, p-type conductivity, and semi-insulating properties.
  • the case where the C-plane GaN substrate of the embodiment is n-type conductive will be described as follows.
  • the resistivity at room temperature of the n-type C-plane GaN substrate of the embodiment is preferably 2.0 ⁇ 10 ⁇ 2 ⁇ cm or less.
  • the resistivity is preferably 2 ⁇ 10 ⁇ when it is necessary to particularly consider the influence of dopant addition on the quality of the GaN crystal constituting the substrate. It is set to 3 ⁇ cm or more, more preferably 5 ⁇ 10 ⁇ 3 ⁇ cm or more.
  • the n-type carrier concentration at room temperature determined based on the Hall effect measurement by the van der Pauw method of the n-type C-plane GaN substrate of the embodiment is preferably 1 ⁇ 10 18 cm ⁇ 3 or more, more preferably 2 ⁇ It is 10 18 cm ⁇ 3 or more, more preferably 3 ⁇ 10 18 cm ⁇ 3 or more.
  • the n-type carrier concentration may be 5 ⁇ 10 18 cm ⁇ 3 or more. From the viewpoint of electrical characteristics, there is no upper limit to the carrier concentration.
  • the carrier concentration is preferably 1 ⁇ 10 20 cm ⁇ 3 or less, more preferably 5 ⁇ 10 19 cm ⁇ 3.
  • Hall effect measurement by the van der Pauw method is performed by using indium solder or the like at the four corners of a plate-shaped test piece having a main surface of a square of 1 ⁇ 1 cm 2 manufactured by cutting a C-plane GaN substrate. This can be done by bonding the lead wires.
  • the above-described resistivity and carrier concentration can be set so that the Hall mobility is 120 cm 2 / V ⁇ s or more, more preferably 150 cm 2 / V ⁇ s or more.
  • the concentration of various impurities contained in the GaN crystal is generally measured by secondary ion mass spectrometry (SIMS).
  • the impurity concentration mentioned below is a value at a portion where the depth from the substrate surface is 1 ⁇ m or more, as measured by SIMS.
  • the concentration of alkali metal and alkaline earth metal is preferably less than 1 ⁇ 10 16 atoms / cm 3 , more preferably less than 1 ⁇ 10 15 atoms / cm 3 .
  • GaN crystals grown monomonothermally in Pt (platinum) capsules using ammonium halide as a mineralizer Li (lithium), Na (sodium), Each concentration of K (potassium), Mg (magnesium), and Ca (calcium) is usually less than 1 ⁇ 10 16 atoms / cm 3 .
  • the C-plane GaN substrate of the embodiment may contain halogen derived from a mineralizer used during crystal growth.
  • a GaN crystal grown using NH 4 F as a mineralizer is 5 ⁇ 10 14 atoms / cm 3 or more and less than 1 ⁇ 10 16 atoms / cm 3 , 1 ⁇ 10 16 atoms / cm 3 or more and 1 ⁇ 10 17.
  • F fluorine
  • concentration such as less than atoms / cm 3 .
  • concentration of I (iodine) in GaN crystals grown ammonothermally using NH 4 F and NH 4 I as mineralizers is usually 1 It is less than ⁇ 10 16 atoms / cm 3 .
  • the H concentration in the C-plane GaN substrate of the embodiment may be 5 ⁇ 10 17 atoms / cm 3 or more.
  • the H concentration is usually 10 21 atoms / cm 3 or less, and may be 5 ⁇ 10 20 atoms / cm 3 or less, 1 ⁇ 10 20 atoms / cm 3 or less, or 5 ⁇ 10 19 atoms / cm 3 or less.
  • the n-type impurities that the C-plane GaN substrate of the embodiment may contain are, for example, O (oxygen), Si (silicon), Ge (germanium), S (sulfur), but are not limited thereto. is not.
  • the C-plane GaN substrate of the embodiment may be an n-type conductive substrate having an O concentration higher than the n-type carrier concentration at room temperature. In that case, the carrier concentration is usually 20 to 70% of the O concentration.
  • an infrared absorption peak attributed to a gallium vacancy-hydrogen complex can be observed at 3140 to 3200 cm ⁇ 1 .
  • the C-plane GaN substrate of the embodiment can be preferably used for manufacturing a nitride semiconductor device. Normally, one or more nitride semiconductors are epitaxially grown on the C-plane GaN substrate of the embodiment to form an epitaxial substrate having a semiconductor device structure.
  • a vapor phase method such as MOCVD method, MBE method, pulse vapor deposition method and the like suitable for forming a thin film can be preferably used, but is not limited thereto.
  • the semiconductor device structure can be formed on either a gallium polar surface or a nitrogen polar surface. After a semiconductor process including etching and application of a structure such as an electrode or a protective film is performed, the epitaxial substrate is divided into a nitride semiconductor device chip.
  • the C-plane GaN substrate of the embodiment is also applicable to applications such as SAW (Surface Acoustic Wave) devices, vibrators, resonators, oscillators, MEMS (Micro Electro Mechanical System) parts, voltage actuators, artificial photosynthetic device electrodes, etc. Is possible.
  • SAW Surface Acoustic Wave
  • vibrators vibrators
  • resonators oscillators
  • MEMS Micro Electro Mechanical System
  • a GaN layer bonded substrate can be manufactured using the C-plane GaN substrate of the embodiment.
  • the GaN layer bonded substrate is a composite substrate having a structure in which a GaN layer is bonded to a different composition substrate having a chemical composition different from that of GaN, and can be used for manufacturing a light emitting device and other semiconductor devices.
  • the different composition substrate sapphire substrate, AlN substrate, SiC substrate, ZnSe substrate, Si substrate, ZnO substrate, ZnS substrate, quartz substrate, spinel substrate, carbon substrate, diamond substrate, Ga 2 O 3 substrate, ZrB 2 substrate, Mo Examples include a substrate, a W substrate, and a ceramic substrate.
  • the GaN layer bonded substrate typically has a step of implanting ions in the vicinity of the main surface of the GaN substrate, a step of bonding the main surface side of the GaN substrate to a different composition substrate, and an ion-implanted region.
  • the GaN substrate is cut into two parts to form a GaN layer bonded to the different composition substrate in this order.
  • the GaN substrate is mechanically cut to form a GaN layer bonded to the different composition substrate. A method has also been developed.
  • the C-plane GaN substrate according to the embodiment can be used as a seed when growing a bulk GaN crystal using various methods.
  • Bulk GaN growth methods include HVPE (hydride vapor phase epitaxy), sublimation, ammonothermal, and Na flux methods, as well as THVPE (Tri-Halide Vapor Phase Epitaxy), OVPE (Oxide Vapor Phase Epitaxy).
  • THVPE Tri-Halide Vapor Phase Epitaxy
  • OVPE Organic Vapor Phase Epitaxy
  • a method or the like can also be preferably used.
  • the THVPE method is a vapor phase growth method of a GaN crystal using GaCl 3 and NH 3 as raw materials. For details, see, for example, International Publication No. WO2015 / 037232.
  • the OVPE method is a vapor phase growth method of GaN using Ga 2 O and NH 3 as raw materials. For details, see, for example, M. Imade, et al., Journal of Crystal Growth, 312 (2010) 676-679. You can refer to it.
  • a growth apparatus of the type shown in FIG. 15 can be preferably used.
  • the feedstock polycrystalline GaN produced by a method of reacting gaseous GaCl obtained by bringing HCl gas into contact with simple substance Ga under heating and NH 3 gas can be preferably used.
  • NH 4 F can be preferably used as the mineralizer.
  • NH 4 F may be used in combination with one or more ammonium halides selected from NH 4 Cl, NH 4 Br and NH 4 I.
  • NH 4 F and NH 4 I may be used in combination.
  • the concentration of NH 4 F can be 0.1 to 1% in terms of a molar ratio to NH 3 .
  • concentration of ammonium halide other than NH 4 F can be 1 to 5% in terms of a molar ratio to NH 3 .
  • the pressure and temperature can be set, for example, within a range of 100 to 250 MPa and within a range of 550 to 650 ° C., but are not limited thereto.
  • Bulk GaN crystals grown using the C-plane GaN substrate according to the embodiment as a seed can be sliced in arbitrary directions to produce GaN substrates having various plane orientations.
  • the C-plane GaN substrate according to the embodiment is a first generation substrate and a C-plane GaN substrate manufactured from a bulk GaN crystal grown using the first generation substrate as a seed is a second generation substrate, the first generation substrate is used.
  • a second generation substrate may have a dislocation array on its main surface similar to the dislocation array that the first generation substrate has on its main surface.
  • Embodiments of the invention can include the second generation substrate.
  • the fourth generation C-plane GaN substrate manufactured from can also have a dislocation array on the main surface similar to the dislocation array that the first generation substrate has on the main surface.
  • Embodiments of the invention can include the third generation C-plane GaN substrate and the fourth generation C-plane GaN substrate.
  • GaN seed 11 nitrogen polar surface 12 gallium polar surface 13 side surface 20 pattern mask 21 linear opening 211 first linear opening 212 second linear opening 30 GaN crystal G gap T through hole V void K intersection 40 C-plane GaN substrate 41 Nitrogen polar surface 42 Gallium polar surface 43 Side surface R1 N surface growth region R2 Lateral growth region 100 Crystal growth apparatus 101 Autoclave 102 Capsule 102a Raw material dissolution zone 102b Crystal growth zone 103 Baffle 104 Pt wire 105 Vacuum pump 106 Ammonia cylinder 107 Nitrogen cylinder 108 Valve 109 Mass flow meter S Seed FS Feedstock

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Abstract

La présente invention consiste principalement à fournir un nouveau procédé de croissance d'un cristal (GaN) convenant comme matériau pour un substrat (GaN) comportant un substrat (GaN) en plan (C). Un autre objet de la présente invention consiste à fournir un nouveau substrat (GaN) en plan (C) qui peut être convenablement utilisé pour fabriquer un dispositif semi-conducteur nitrure, etc. L'invention concerne également un procédé de croissance d'un cristal (GaN), le procédé comprenant : une première étape de préparation d'une semence (GaN) possédant une surface polaire azotée; une seconde étape de mise en place d'un masque de motif sur la surface polaire azotée de la semence (GaN), où le masque de motif est fourni avec un profil d'ouverture périodique qui est composé d'ouvertures linéaires et qui comporte des intersections, et le masque de motif est disposé de sorte que l'angle entre le sens longitudinal d'au moins une portion des ouvertures linéaires et la direction de la ligne d'intersection entre la surface polaire azotée et la surface (M) se situe à l'intérieur de ±3 °; et une troisième étape de croissance de manière ammonothermique du cristal (GaN) sur la surface polaire azotée de la semence (GaN) à travers le masque de motif, un espace étant formé entre le cristal (GaN) et le masque de motif. Un nouveau substrat (GaN) en plan (C) qui peut être convenablement utilisé pour la fabrication d'un dispositif semi-conducteur nitrure, etc. est également fourni.
PCT/JP2017/028483 2016-08-08 2017-08-04 PROCÉDÉ DE CROISSANCE DE CRISTAL (GaN) ET SUBSTRAT (GaN) EN PLAN (C) WO2018030312A1 (fr)

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JP2018533015A JP6981415B2 (ja) 2016-08-08 2017-08-04 ＧａＮ結晶成長方法およびＣ面ＧａＮ基板
CN201780048862.3A CN109563641B (zh) 2016-08-08 2017-08-04 GaN结晶生长方法和C面GaN基板
CN202110907715.5A CN113604885B (zh) 2016-08-08 2017-08-04 C面GaN基板和氮化物半导体器件的制造方法
US16/270,454 US10720326B2 (en) 2016-08-08 2019-02-07 Method for growing GaN crystal and C-plane GaN substrate
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US11466384B2 (en) 2019-01-08 2022-10-11 Slt Technologies, Inc. Method of forming a high quality group-III metal nitride boule or wafer using a patterned substrate
WO2020241760A1 (fr) * 2019-05-30 2020-12-03 三菱ケミカル株式会社 Tranche de substrat de gan et son procédé de fabrication
TW202117106A (zh) * 2019-07-01 2021-05-01 日商三菱化學股份有限公司 塊狀GaN結晶、c面GaN晶圓及塊狀GaN結晶的製造方法
WO2021162727A1 (fr) 2020-02-11 2021-08-19 SLT Technologies, Inc Substrat de nitrure du groupe iii amélioré, son procédé de fabrication et procédé d'utilisation
US11721549B2 (en) 2020-02-11 2023-08-08 Slt Technologies, Inc. Large area group III nitride crystals and substrates, methods of making, and methods of use
CN113430641B (zh) * 2021-06-24 2022-03-11 齐鲁工业大学 阻碍半极性面氮化镓生长并制备自剥离氮化镓晶体的方法

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CN113604885A (zh) 2021-11-05
US20200303187A1 (en) 2020-09-24
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US10720326B2 (en) 2020-07-21
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